Azopyridone dyes

ABSTRACT

A water-soluble compound of Formula (1) which is useful for coloring e.g. cellulosic materials, animal furs and animal skins such as leather. ##STR1## wherein: A is optionally substituted phenylene or naphthylene; 
     X is a cellulose-reactive group; 
     p is greater than or equal to 1; 
     T 1  and T 2  are each independently selected from H, CN, CO 2  R 2 , CONR 2  R 3 , COR 2 , alkyl, aralkyl, cycloalkyl, aryl or a heterocyclic radical, which are unsubstituted or substituted; 
     Z is a divalent linking group containing from 2 to 6 carbon atoms; 
     n is from 2 to 6; 
     R 1  is H or sulpho; and 
     R 2  and R 3  are each independently H or C 1-6  -alkyl; 
     and salts thereof.

This invention relates to a compound suitable for use as a reactive dye for the coloration of materials having --OH or --NH-- groups, to a method for its manufacture and to a method for the coloration of materials using the compound.

According to the present invention there is provided a water-soluble compound of Formula (1) or salt thereof: ##STR2## wherein: A is optionally substituted phenylene or naphthylene;

X is a cellulose-reactive group;

X¹ is H or a cellulose-reactive group;

p is greater than or equal to 1;

T¹ and T² are each independently H, CN, CO₂ R², CONR² R³, COR², alkyl, aralkyl, cycloalkyl, aryl or a heterocyclic radical;

Z is a divalent linking group containing from 2 to 6 carbon atoms;

n is from 2 to 6;

R¹ is H or sulpho;

R² and R³ are each independently H or C₁₋₆ -alkyl.

The optional substituents preset on A are preferably selected from --Cl, --Br, --C₁₋₄ -alkyl, --OH, --O--C₁₋₄ -alkyl, --CN, --NO₂, --NH₂ and --NHCOCH₃, and especially sulpho and carboxy.

The group represented by X¹ -A- is preferably a phenyl or naphthyl group having 1, 2 or 3-sulpho substituents. As examples of preferred groups represented by X¹ -A- there may be mentioned 2-, 3- or 4-sulphophenyl; 2,5- or 2,4-disulphophenyl; 1,5-disulphonaphth-2-yl; 2-methyl-4-sulphophenyl; 2-methoxy-5-sulphophenyl; 4-methoxy-2-sulphophenyl; 2-methyl-5-sulphophenyl; 1-sulphonaphth-2-yl; 1,5,7-trisulphonaphth-2-yl; 3,6,8-trisulphonaphth-2-yl; 4,8-disulphonaphth-2-yl; 6-sulphonaphth-2-yl; 4,8-disulphonaphth-1-yl; and 2,5,7-trisulphonaphth-1-yl.

T¹ is preferably C₁₋₄ -alkyl, especially methyl. T² is preferably CN, CO₂ R², CONR² R³, COR², C₁₋₄ -alkyl or H, and more especially H or methyl. R² and R³ are preferably H or C₁₋₄ -alkyl.

Z is preferably a divalent linking group containing from 2 to 4 carbon atoms such as C₁₋₄ -alkylene. As examples of Z there may be mentioned --CH₂ CH₂ --, --CH₂ CH₂ CH₂ --, --CH₂ CH(CH₃)CH₂ --, and --CH₂ CH₂ CH₂ CH₂ CH₂ --.

It is preferred that n is from 2 to 4, especially 2, and R¹ is preferably sulpho.

The compound of the present invention preferably contains a total of at least 3 sulphonic acid groups, more preferably from 3 to 10 sulphonic acid groups.

It will be appreciated that the azo pyridone entity in Formula (1) may exist in tautomeric forms other than that shown, and these are included as an aspect of the present invention.

Although formulae in the present specifiable are drawn in their free acid form it is intended that the invention also relates to the compound in salt form, preferably in their sodium, potassium, lithium or mixed sodium/lithium salt form.

The term "cellulose-reactive group" means a group whose presence in the compound renders it capable of forming a covalent bond with --OH or --NH-- groups present in textile materials, especially in the presence of alkali, such as cotton, jute, hemp, and flax, or in leather.

The cellulose-reactive group is preferably a heterocyclic radical having two or three nitrogen atoms in the heterocyclic ring and at least one labile substituent attached to a carbon atom in the heterocyclic ring. The preferred cellulose-reactive groups are of the pyrimidinyl and triazinyl series. A labile substituent is one capable of being replaced by nucleophilic substitution during exhaust dyeing to form a covalent bond between the heterocyclic ring and a nucleophile. Preferred labile substituents include fluorine, bromine, and especially chlorine and quaternary ammonium groups.

When X¹ is a heterocyclic radical having two or three nitrogen atoms in the heterocyclic ring it is preferably attached to A via an amino group. As specific examples of such cellulose-reactive heterocyclic radicals there may be mentioned

5- or 6-(sulphonyl or carbonyl)-2,3-dichloroquinoxaline;

6- or -7-sulphonyl-2,4-dichloroquinazoline;

7- or -8-sulphonyl-2,4,6-trichloroquinazoline;

6-sulphonyl-2,4,7- or 2,4,8-trichloroquinazoline;

6-carbonyl-2,4-dichloroquinazoline;

6-carbonyl-1,4-dichlorophthalazine;

4,5-dichloropyridazinyl;

5-carbonyl-2,4-dichloropyrimidine;

1-(phenyl-4'-carbonyl)-4,5-dichloropyridazone;

1-(phenyl-4'-sulphonyl)-4,5-dichloropyridazone;

2,4- and/or 2,6-dichloro- (or bromo)-pyridin-6-(and/or -4)yl;

trichloropyrimidinyl;

tribromopyridinyl;

dichloro-5-(cyano, nitro, methyl or methoxycarbonyl)pyrimidinyl;

4-carbonyl-2-methylsulphonyl-6-chloropyrimidine;

5-chloro-6-methyl-2-methylsulphonylpyrimidin-4-yl.

It is preferred that the cellulose reactive groups in compounds of the present invention are each independently an s-triazin-2-yl group having a labile substituent on one or both of the 4- and 6-positions. In this instance a wide range of labile substituents are envisaged, such as activated aryloxy or various groups linked through a sulphur atom and halo substituents, but the preferred labile substituents are F or Br, and especially Cl or a quaternary ammonium group. As examples of quaternary ammonium groups there may be mentioned tri-lower alkyl ammonium, e.g. (CH₃)₃ N⁺ -- and optionally substituted pyridinium groups especially those derived from pyridine carboxylic acids in particular from nicotinic acid and isonicotinic acid.

When the s-triazin-2-yl group has a labile substituent on only one of the 4- or 6-positions then the remaining 4- or 6-position is substituted by a non-labile substituent, such as a non-reactive substituent, or is linked via a diamino linking group to another cellulose reactive group. The diamino linking group is preferably a group of the formula --N(R⁴)--L--N(R⁵)-- wherein L is a divalent organic linking group, R⁴ and R⁵ are each independently selected from H and C₁₋₄ -alkyl, or R⁴ and R⁵ together with --N--L--N-- form a 5 or 6 membered ring, which is preferably a piperazine ring.

As examples of non-reactive substituents there may be mentioned alkylthio groups, alkoxy groups and optionally substituted amino groups. Preferred forms of these non-reactive substituents include C₁₋₄ -alkoxy groups such as methoxy, ethoxy, n-propoxy, iso-propoxy and butoxy, and C₁₋₄ -alkoxy-C₁₋₄ -alkoxy groups such as beta-methoxy-ethoxy and beta-ethoxyethoxy; C₁₋₄ -thioalkyl groups; --NH₂ ; C₁₋₄ -alkylamino groups such as methylamino, ethylamino and butylamino, di(C₁₋₄ -alkyl)amino groups such as dimethylamino, diethylamino, N-methyl-N-ethylamino and dibutylamino; alkylamino groups which are substituted by, for example, OH, CN, halo or sulpho, such as beta-hydroxyethylamino, di(beta-hydroxyethyl)amino, beta-cyanoethylamino, di(beta-cyanoethyl)amino, beta-sulphoethylamino, beta-hydroxypropylamino, N-(beta-hydroxybutyl)-N-ethylamino and N-(beta-hydroxyethyl)-N-methylamino; cycloalkylamino such as cyclohexylamino; cyclic amino groups such as morpholino and piperazino; naphthylamino substituted by 1, 2 or 3 sulpho groups; and optionally substituted phenylamino groups.

An especially preferred form of the non-reactive optionally substituted phenylamino group is of the Formula (2): ##STR3## wherein G is H, methyl, ethyl, sulphomethyl, 2-carboxy-, 2-hydroxy- or 2-cyanoethyl and S¹ and S² are each independently selected from CH₃, C₂ H₅, OCH₃, OC₂ H₅, Cl, Br, CN, NO₂, NHCOCH₃ and especially H, carboxy and sulpho.

As specific examples of non-reactive optionally substituted groups of Formula (2) there may be mentioned

anilino,

o, m- or p-sulphoanilino

o-, m- or p-carboxyanilino,

4- or 5-sulpho-2-carboxyanilino,

4- or 5-sulpho-o-tolylamino,

2,4- 2,5- or 3,5-disulphoanilino,

2,4-dicarboxyanilino,

4- or 5-sulpho-2-methoxyanilino,

N-methyl-o-, m- or p-sulphoanilino,

N-omega-sulphomethylanilino,

N-(beta-hydroxyethyl)-3-sulphoanilino.

Further classes of compounds according to the present invention include a compound of Formula (1) in which X is of formula --L--SO₂ CH₂ CH₂ OSO₃ H or --L--SO₂ CH═CH wherein L is a divalent organic linking group and those in which X¹ is H or SO₂ CH₂ CH₂ OSO₃ H or SO₂ CH═CH.

The identity of the divalent organic linking group L is not critical providing it does not adversely interfere with the performance of the dyestuff. As examples of divalent organic linking groups represented by L there may be mentioned:

(a) divalent aliphatic radicals, preferably those containing from 2 to 6 carbon atoms, such as ethylene, trimethylene, methylethylene, tetramethylene, alpha:beta-dimethylethylene and hexamethylene radicals;

(b) divalent aromatic radicals in which at least one of the terminal links is through an aliphatic carbon atom, for example as in the divalent benzyl --C₆ H₄.CH₂ -- or the xylylene --CH₂ C₆ H₄ CH₂ -- group;

(c) divalent monocyclic or fused polycyclic aromatic radicals, for example optionally substituted phenylene or optionally substituted naphthylene such as

    ______________________________________                                         1,3- or 1,4-phenylene                                                                            2-nitro-1,4-phenylene                                        3-sulpho-1,4-phenylene                                                                           4-methoxy-1,3-phenylene                                      4-sulpho-1,3-phenylene                                                                           4-nitro-1,3-phenylene                                        2-carboxy-1,4-phenylene                                                                          2-chloro-1,4-phenylene                                       4-carboxy-1,3-phenylene                                                                          3,7-disulpho-1,5-naphthylene                                 2-methoxy-1,4-phenylene;                                                       ______________________________________                                    

(d) divalent radicals wherein the terminal bonds are attached to carbon atoms of two phenyl or naphthalene nuclei which are joined together either through a direct link or through an atom or chain of atoms which optionally form a homocyclic or heterocyclic ring, for example radicals of the formula: ##STR4## wherein B is --S--, --O--, --SO₂ --, --CO--, --CH₂ --, --CH₂ CH₂ --, --NH--, --NHCONH--, a direct link or preferably --CH═CH--.

As will be understood, a homocyclic ring is a ring of carbon atoms, and a heterocyclic ring is a ring containing at least one hetero atom, such as O, N or S.

As specific examples of divalent radicals defined in (d) there may be mentioned divalent:

    ______________________________________                                         diphenyl       azobenzene                                                      diphenyloxide  diphenyloxadiazole                                              diphenylamine  benzanilide                                                     diphenylsulphide                                                                              diphenylurea                                                    diphenylsulphone                                                                              1,2-bis(phenylcarbamyl)ethylene                                 diphenylmethane                                                                               1,4-bis-(phenylcarbamyl)butadiene                               diphenylketone 1,2-bis-(phenylcarbamyl)ethane                                  diphenylethane 1,3-bis-(phenylcarbamyl)propane                                 diphenylethylene                                                                              stilbene; and                                                   ______________________________________                                    

(e) nuclear substituted derivatives of the above, for example, containing COOH, methyl, nitro, chloro, sulpho atoms or groups as substituents on the phenyl or naphthalene nuclei.

When the cellulose-reactive group X in the compound of Formula (1) is S-traizin-2-yl having a labile group substituent on one ring carbon atom, and the other ring carbon atom is linked via a diamino linking group to another cellulose-reactive group, the compound is preferably of Formula (3).

Accordingly the present invention provides a compound which, in the free acid form, if of Formula (3): ##STR5## wherein each A, T¹, T², Z, n, R¹, R⁴, R⁵ and L independently is as hereinbefore defined; and W is a labile substituent.

It is preferred that L is 2,2'-disulphostilben-4,4'-yl and that W is halo or quaternary ammonium, especially chloro, nicotin-1-yl or iso-nicotin-1-yl.

Although the two groups attached to L in Formula (3) can be different it is preferred that they are identical.

In a compound of Formula (3) it is preferred that each A independently is a phenyl or naphthyl group optionally having one or more, preferably from 1 to 3, substituents selected from --Cl, --Br, --C₁₋₄ -alkyl, hydroxy, --O--C₁₋₄ -alkyl, --CN, --NO₂, --NH₂ and --NHCOCH₃ and especially --H, -sulpho and -carboxy.

As examples of amines of the formula A--NH₂, from which A may be derived, there may be mentioned

    ______________________________________                                         aniline,          2-sulpho-4-methylaniline,                                    aniline-2-sulphonic acid,                                                                        2-sulpho-5-methylaniline,                                    aniline-3-sulphonic acid,                                                                        2-methoxy-5-sulphoaniline,                                   aniline-4-sulphonic acid,                                                                        2-sulpho-4-methoxyaniline,                                   aniline-2,4-disulphonic acid,                                                                    2-chloro-4-sulphoaniline,                                    aniline-2,5-disulphonic acid,                                                                    2,5-dichloro-4-sulphoaniline,                                aniline-3,5-disulphonic acid,                                                                    2-chloro-5-sulphoaniline,                                    2-methyl-4-sulphoaniline,                                                                        2-sulpho-4-nitroaniline,                                     2-methyl-5-sulphoaniline,                                                                        2-sulpho-5-nitroaniline,                                     2-carboxy-5-sulphoaniline,                                                     2-aminonaphthalene-1,5-disulphonic acid,                                       2-aminonaphthalene-1-sulphonic acid,                                           2-aminonaphthalene-1,5,7-trisulphonic acid,                                    2-aminonaphthalene-3,6,8-trisulphonic acid,                                    2-aminonaphthalene-4,8-disulphonic acid,                                       2-aminonaphthalene-5,7-disulphonic acid,                                       2-aminonaphthalene-6-sulphonic acid,                                           1-aminonaphthalene-4-sulphonic acid,                                           1-aminonaphthalene-5-sulphonic acid,                                           1-aminonaphthalene-6-sulphonic acid,                                           1-aminonaphthalene-7-sulphonic acid,                                           1-aminonaphthalene-4,8-disulphonic acid,                                       1-aminonaphthalene-3,8-disulphonic acid,                                       1-aminonaphthalene-2,5,7-trisulphonic acid, and                                1-aminonaphthalene-3,5,7-trisulphonic acid.                                    ______________________________________                                    

It has been found that compositions containing two compounds of Formula (1) which are identical except that in the first compound R¹ is H and in the second compound R¹ is sulpho also are of a value for the coloration of cellulosic textile materials or leathers.

Accordingly, a second aspect of the invention relates to compositions containing a first and second compound of Formula (1) wherein X¹, A, T¹, T²,Z, X, p and n are the same in the first and second compound, and R¹ in the first compound is H and R¹ in the second compound is sulpho.

In mixtures of the second aspect of the invention the ratio of compound in which R¹ is H to the compound in which R¹ is sulpho may be varied between wide limits, depending upon the conditions employed when preparing the dyes. It is preferred that the ratio of compound in which R¹ is H to compound in which R¹ is sulpho is in the range of 90:10 to 10:90, more preferably 90:10 to 50:50, especially 80:20 to 70:30, and more especially about 75:25.

A compound and mixtures of compounds according to the invention wherein X¹, A, X, R¹, R⁴, R⁵, T¹, T², n and L are as hereinbefore defined can be prepared by diazotising an amine of formula X¹ --A--NH₂ and coupling to a compound of mixture of compounds of Formula (4) ##STR6## followed by condensation with a cellulose-reactive compound of formula X--X² in which X is as defined above and X² is a labile group capable of being displaced by nucleophilic substitution.

A compound of Formula (1) in which the component R¹ is sulpho can be prepared by purifying mixtures of compounds containing R¹ ═H and R¹ =sulpho, for example using chromatographic techniques such as preparative HPLC.

In the above process it is convenient to use a mixture of compounds of Formula (4) in which R¹ is H and SO₃ H in the ratio of 10:90 to 90:10, preferably in the range of 90:10 to 50:50, especially in the range 80:20 to 70:30, more especially about 75:25.

A convenient process for preparing a compound of Formula (4) in which R¹ is sulpho is by stirring the corresponding compound in which R¹ is H in 98% sulphuric acid at a temperature of 0°-5° C.

A preferred process for preparing the mixtures of Formula (4) in which T² is H or C₁₋₄ -alkyl and in which R¹ is sulpho and H is by stirring the corresponding 3-cyanopyridone of Formula (5) (wherein R¹ is H) in 78% sulphur acid at a temperature of above 100° C., especially 125°-1352 C., for several hours, preferably approximately 3 hours. ##STR7##

This typically produces a mixture in which the ratio of R¹ =H to R¹ =sulpho is in the range of 80:20 to 70:30. Mixtures in which the percentage of the component in which R¹ =H is decreased and the percentage of R¹ =sulpho is increased can be made by stirring the mixture of Formula (5) (obtained as described above by treatment with 78% sulphuric acid) in 20% oleum at 0°-5° C.

Mixtures in which the percentage of the compound in which R¹ is sulpho is increased can also be made by taking the dyebase obtained by diazotising an amine of formula X¹ ANH₂ and coupling to a mixture of Formula (4) and stirring this in 98% sulphuric acid at 0°-5° C.

A compound of mixtures of Formula (3) in which the two groups attached to L are identical can be conveniently prepared by diazotisation of an amine of formula A--NH₂, coupling to a compound or mixture of Formula (4) to give an azo pyridone. An amine of formula HN(R⁴)--L--N(R⁵)H is condensed with at least two equivalents of triazine compound having a group represented by W on each ring carbon atom, and the product condensed, preferably in the presence of base, with approximately two equivalents of the above azo pyridone to give a compound of mixture of Formula (3).

A compound or mixture of compounds of Formula (3) in which the two groups attached to L are different can be prepared by independently diazotising two different amines of formula A--NH₂, independently coupling these amines to compounds or mixtures of Formula (4) to give different azo pyridones which are condensed with an amine as described above to give a mixture from which can be isolated a compound or mixture of Formula (3) in which the two groups attached to L are different.

It is preferred that (i) the group W in the above processes is halo, especially chloro, and, (ii) when W in the final dyestuff is quaternary ammonium, this is prepared by reacting the product of the above processes with the appropriate amine.

The compound of the invention is characterised by its good dyeing properties, and in particular its substantivity, fixation efficiency and build up when applied to cellulosic materials. A particularly notable feature of a dye of the present invention is its good stability under alkaline conditions used during exhaust dyeing.

According to a further aspect of the present invention there is provided a process for the coloration of materials, particularly materials having a --OH or --NH-- group, such as cellulosic material (e.g. cotton), an animal fur, or an animal skin (e.g. leather), by applying thereto a compound of Formula (1) or of Formula (3), or a composition containing at least two compounds of Formula (1) or of Formula (3). A still further aspect of the invention comprises such materials when dyed with a compound or composition of Formula (1) or Formula (3).

The invention is further illustrated by the following Examples in which all parts and percentages are by weight unless otherwise indicated.

EXAMPLE 1 Preparation of the compound of Formula (6) in which W is Cl ##STR8## (i) Diazotisation

81.4 Parts of 2-aminonaphthalene-1,5-disulphonic acid were added to 1500 parts of water and 40 parts of hydrochloric acid (S.G. 1.18) and the mixture cooled to 0°-5° C. with stirring. 101 Parts of 2N sodium nitrite solution were added dropwise over 1 hour. The slight excess of nitrous acid was then destroyed by the addition of 10% aqueous sulphamic acid to give a yellow diazo suspension.

(ii) Preparation of coupling component

50 Parts of 1-beta-(hydroxyethylamino)ethyl-3-cyano-6-hydroxy-4-methyl-2-oxo-1H-pyridine were added to 80 parts of well stirred 78% sulphuric acid at such a rate that the temperature did not exceed 40° C. The mixture was then heated to 130° C. and stirred at 130°±5° C. for 3 hours before cooling to ambient temperature and adding to 2000 parts of ice water. The resultant sulphuric acid solution contained a mixture of 1-beta-(hydroxyethylamino)ethyl-6-hydroxy-4-methyl-2-oxo-1H-pyridine and 1-beta-(sulphatoethylamino)ethyl-6-hydroxy-4-methyl-2-oxo-1H-pyridine in the ratio of approximately 3:1.

(iii) Coupling

The above yellow diazo suspension from stage (i) was added to the sulphuric acid solution from stage (ii) and the mixture stirred for 4 hours at 0°-5° C. without pH adjustment. After allowing the temperature to rise to ambient the pH was adjusted to 7 with sodium hydroxide, 15% w/v sodium chloride was added and stirring continued for a further 1 hour. The precipitated solid was collected by filtration, reslurried in water and dialysed to remove inorganic salts. The suspension was then evaporated to dryness to give an azopyridone dyebase.

(iv) Preparation of linking group

30 Parts of 4,4'-diaminostilbene-2,2'-disulphonic acid were suspended in 500 parts of water and the pH adjusted to 7 with sodium hydroxide. The solution was added to a stirred suspension of 40.6 parts of cyanuric chloride in 40 parts of acetone and 150 parts of ice. The mixture was stirred for a further 11/2 hours whilst maintaining the pH between 6.5 and 7 with 2N sodium carbonate solution as required. The precipitate solid was collected by filtration, washed with ice cold water and reslurried in acetone. The product was again collected by filtration, washed with acetone, dried and mixed with 10 parts of mixed phosphate buffer (2 parts of potassium dihydrogen phosphate and 1 part of disodium hydrogen phosphate) to give 4,4'-bis-dichlorotriazinylaminostilbene-2,2'-disulphonic acid.

(v) Condensation of azopyridone dyebase and linking group

10 Parts of 4,4'-bis-dichlorotriazinylaminostilbene-2,2'-disulphonic acid from step (iv) were added to 11 parts of the above azopyridone dyebase from step (iii) in 800 parts of water and the mixture stirred at ambient temperature whilst maintaining the pH between 6.5 and 7 with 2N sodium carbonate as required. After stirring for 4 hours at pH 6.5-7 the temperature was increased to 40° C. and stirring continued for a further 12 hours to complete the condensation. The solution was concentrated to 150 parts and 10% w/v sodium chloride added. The title product was precipitated as a solid and collected by filtration, washed with acetone and dried.

When applied to cellulose fibres in conjunction with an acid binding agent, the fibres were dyed in bright greenish-yellow shades having good fastness to wet treatments and to light.

EXAMPLE 2 Preparation of compound of Formula (6) in which W is 3-carboxypyridinium

To a suspension of 77.5 parts of the product of Example 1 in 1000 parts of water were added a solution ob 12.3 parts of nicotinic acid in 500 parts of water at pH 7. The stirred mixture was then heated to 80° C. whilst maintaining the pH between 6.7 and 7. Heating at 80° C. was continued for a further 24 hours after which time no starting material of Formula (6) in which W is Cl remained (according to HPLC analysis). The solution was concentrated, dialysed and evaporated to dryness to give the title product.

When the title product was applied to cellulose fibres in conjunction with an acid binding agent, the fibres were dyed in strong bright greenish-yellow shades having good build-up and good fastness to wet treatments and to light.

EXAMPLE 3 Preparation of compound of Formula (6) in which W is 4-carboxypyridinium

The 12.3 parts of nicotinic acid in Example 2 can be replaced with 12.3 parts of iso-nicotinic acid to give a dyestuff having similar properties.

EXAMPLE 4

When the dyestuff prepared in Example 1 is applied to leather under slightly acidic conditions a bright greenish-yellow shade is obtained with excellent fastness to wet treatments and to light.

EXAMPLE 5 to 44

Further dyes of the invention can be prepared by diazotising the amine listed in column 1, coupling with the mixed pyridines listed in column 2, followed by condensation with the compound listed in column 3, reaction with the amine on linking group listed in column 4, and quaternisation using an analogous method to that described in Example 2 with the reagent listed in column 5.

    __________________________________________________________________________     Example                                                                             1            2             3    4          5                              __________________________________________________________________________      5   Aniline-2-sulphonic acid                                                                    1-beta-(hydroxyethylamino)                                                                   Cyanuric                                                                            4,4'-diaminostilbene                                                                      nicotinic acid                                   ethyl-6-hydroxy-4-methyl-                                                                    Chloride                                                                            2,2'-disulphonic                                            2-oxo-1H pyridine (I)                                                                             acid                                                        1-beta-(sulphatoethylamino)                                                    ethyl-6-hydroxy-4-methyl-                                                      2-oxo-1H pyridine (II)                                                         I 70% II 30%                                                  6   Aniline-3-sulphonic acid                                                                    1-beta-(hydroxyethylamino)                                                                   Cyanuric                                                                            4,4'-diaminostilbene                                                                      iso-nicotinic                                    ethyl-6-hydroxy-4-methyl-                                                                    Chloride                                                                            2,2'-disulphonic                                                                          acid                                             2-oxo-1H pyridine (I)                                                                             acid                                                        1-beta-(sulphatoethylamino)                                                    ethyl-6-hydroxy-4-methyl-                                                      2-oxo-1H pyridine (II)                                                         I 70% II 30%                                                  7   Aniline-4-sulphonic acid                                                                    1-beta-(hydroxyethylamino)                                                                   Cyanuric                                                                            4,4'-diaminostilbene                                                                      nicotinic acid                                   ethyl-6-hydroxy-4-methyl-                                                                    Chloride                                                                            2,2'-disulphonic                                            2-oxo-1H pyridine (I)                                                                             acid                                                        1-beta-(sulphatoethylamino)                                                    ethyl-6-hydroxy-4-methyl-                                                      2-oxo-1H pyridine (II)                                                         I 70% II 30%                                                  8   Aniline-2,5-disulphonic                                                                     1-beta-(hydroxyethylamino)                                                                   Cyanuric                                                                            4,4'-diaminostilbene                                                                      nicotinic acid                      acid         ethyl-6-hydroxy-4-methyl-                                                                    Chloride                                                                            2,2'-disulphonic                                            2-oxo-1H pyridine (I)                                                                             acid                                                        1-beta-(sulphatoethylamino)                                                    ethyl-6-hydroxy-4-methyl-                                                      2-oxo-1H pyridine (II)                                                         I 70% II 30%                                                  9   Aniline-2,4-disulphonic                                                                     1-beta-(hydroxyethylamino)                                                                   Cyanuric                                                                            4,4'-diaminostilbene                                                                      nicotinic acid                      acid         ethyl-6-hydroxy-4-methyl-                                                                    Chloride                                                                            2,2'-disulphonic                                            2-oxo-1H pyridine (I)                                                                             acid                                                        1-beta-(sulphatoethylamino)                                                    ethyl-6-hydroxy-4-methyl-                                                      2-oxo-1H pyridine (II)                                                         I 70% II 30%                                                 10   2-aminonaphthalene-                                                                         1-beta-(hydroxyethylamino)                                                                   Cyanuric                                                                            ethylene diamine                                                                          nicotinic acid                      1,5-disulphonic acid                                                                        ethyl-6-hydroxy-4-methyl-                                                                    Chloride                                                         2-oxo-1H pyridine (I)                                                          1-beta-(sulphatoethylamino)                                                    ethyl-6-hydroxy-4-methyl-                                                      2-oxo-1H pyridine (II)                                                         I 70% II 30%                                                 11   2-aminonaphthalene-                                                                         1-beta-(hydroxyethylamino)                                                                   Cyanuric                                                                            1,4-phenylene diamine                                                                     --                                  1,5-disulphonic acid                                                                        ethyl-6-hydroxy-4-methyl-                                                                    Chloride                                                         2-oxo-1H pyridine (I)                                                          1-beta-(sulphatoethylamino)                                                    ethyl-6-hydroxy-4-methyl-                                                      2-oxo-1H pyridine (II)                                                         I 70% II 30%                                                 12   2-aminonaphthalene-                                                                         1-beta-(hydroxyethylamino)                                                                   Cyanuric                                                                            1,4-phenylene diamine                                                                     iso-nicotinic                       1,5-disulphonic acid                                                                        ethyl-6-hydroxy-4-methyl-                                                                    Chloride        acid                                             2-oxo-1H pyridine (I)                                                          1-beta-(sulphatoethylamino)                                                    ethyl-6-hydroxy-4-methyl-                                                      2-oxo-1H pyridine (II)                                                         I 70% II 30%                                                 13   2-aminonaphthalene-                                                                         1-beta-(hydroxyethylamino)                                                                   Cyanuric                                                                            1,3-phenylene diamine                                                                     iso-nicotinic                       1,5-disulphonic acid                                                                        ethyl-6-hydroxy-4-methyl-                                                                    Chloride        acid                                             2-oxo-1H pyridine (I)                                                          1-beta-(sulphatoethylamino)                                                    ethyl-6-hydroxy-4-methyl-                                                      2-oxo-1H pyridine (II)                                                         I 70% II 30%                                                 14   2-aminonaphthalene-                                                                         I 50% II 50%  Cyanuric                                                                            4,4'-diaminostilbene                                                                      iso-nicotinic                       1,5-disulphonic acid       Chloride                                                                            2,2'-disulphonic acid                                                                     acid                           15   2-aminonaphthalene-                                                                         I 80% II 20%  Cyanuric                                                                            1,4-phenylenediamine-                                                                     nicotinic acid                      1,5-disulphonic acid       Chloride                                                                            3-sulphonic acid                          16   2-aminonaphthalene-                                                                         I 80% II 20%  Cyanuric                                                                            4,4'-diamino-                                                                             nicotinic acid                      1,5-disulphonic acid       Chloride                                                                            benzanilide                               17   2-aminonaphthalene-                                                                         I 80% II 20%  Cyanuric                                                                            4,4'-diaminodiphanyl                                                                      nicotinic acid                      1,5-disulphonic acid       Chloride                                                                            2,2'-disulphonic                                                               acid                                      18   2-aminonaphthalene-                                                                         1-beta-(hydroxyethylamino)                                                                   Cyanuric                                                                            4,4'-diaminostilbene                                                                      iso-nicotinic                       1,5-disulphonic acid                                                                        ethyl-6-hydroxy-3,4-di                                                                       Chloride                                                                            2,2'-disulphonic                                                                          acid                                             methyl-2-oxo-1H pyridine                                                                          acid                                                        (I)                                                                            1-beta-(sulphatoethylamino)                                                    ethyl-6-hydroxy-3,4-di                                                         methyl-2-oxo-1H pyridine                                                       (II)                                                                           I 70% II 30%                                                 19   2-methylaniline-                                                                            1-beta-(hydroxyethylamino)                                                                   Cyanuric                                                                            4,4'-diaminostilbene                                                                      iso-nicotinic                       5-sulphonic acid                                                                            ethyl-6-hydroxy-3,4-di                                                                       Chloride                                                                            2,2'-disulphonic                                                                          acid                                             methyl-2-oxo-1H pyridine                                                                          acid                                                        (I)                                                                            1-beta-(sulphatoethylamino)                                                    ethyl-6-hydroxy-3,4-di                                                         methyl-2-oxo-1H pyridine                                                       (II)                                                                           I 70% II 30%                                                 20   2-methylaniline-                                                                            1-beta-(hydroxyethylamino)                                                                   Cyanuric                                                                            4,4'-diaminostilbene                                                                      iso-nicotinic                       5-disulphonic acid                                                                          ethyl-6-hydroxy-3,4-di                                                                       Chloride                                                                            2,2'-disulphonic                                                                          acid                                             methyl-2-oxo-1H pyridine                                                                          acid                                                        (I)                                                                            1-beta-(sulphatoethylamino)                                                    ethyl-6-hydroxy-3,4-di                                                         methyl-2-oxo-1H pyridine                                                       (II)                                                                           I 70% II 30%                                                 21   Aniline-2,5-disulphonic                                                                     1-beta-(hydroxyethylamino)                                                                   Cyanuric                                                                            4,4'-diaminostilbene                                                                      nicotinic acid                      acid         ethyl-6-hydroxy-3,4-di                                                                       Chloride                                                                            2,2'-disulphonic                                            methyl-2-oxo-1H pyridine                                                                          acid                                                        (I)                                                                            1-beta-(sulphatoethylamino)                                                    ethyl-6-hydroxy-3,4-di                                                         methyl-2-oxo-1H pyridine                                                       (II)                                                                           I 70% II 30%                                                 22   2-methoxyaniline-                                                                           1-beta-(hydroxyethylamino)                                                                   Cyanuric                                                                            4,4'-diaminostilbene                                                                      nicotinic acid                      5-sulphonic acid                                                                            ethyl-6-hydroxy-3,4-di                                                                       Chloride                                                                            2,2'-disulphonic                                            methyl-2-oxo-1H pyridine                                                                          acid                                                        (I)                                                                            1-beta-(sulphatoethylamino)                                                    ethyl-6-hydroxy-3,4-di                                                         methyl-2-oxo-1H pyridine                                                       (II)                                                                           I 70% II 30%                                                 23   4-methoxyaniline-                                                                           1-beta-(hydroxyethylamino)                                                                   Cyanuric                                                                            4,4'-diaminostilbene                                                                      iso-nicotinic                       2-sulphonic acid                                                                            ethyl-6-hydroxy-3,4-di                                                                       Chloride                                                                            2,2'-disulphonic                                                                          acid                                             methyl-2-oxo-1H pyridine                                                                          acid                                                        (I)                                                                            1-beta-(sulphatoethylamino)                                                    ethyl-6-hydroxy-3,4-di                                                         methyl-2-oxo-1H pyridine                                                       (II)                                                                           I 70% II 30%                                                 24   2-aminonaphthalene-                                                                         1-beta-(hydroxyethylamino)                                                                   Cyanuric                                                                            Aniline-2-sulphonic                                                                       nicotinic acid                      1,5-disulphonic acid                                                                        ethyl-6-hydroxy-4-methyl-                                                                    Chloride                                                                            acid                                                        2-oxo-1H pyridine (I)                                                          1-beta-(sulphatoethylamino)                                                    ethyl-6-hydroxy-4-methyl-                                                      2-oxo-1H pyridine (II)                                                         I 70% II 30%                                                 25   2-aminonaphthalene-                                                                         1-beta-(hydroxyethylamino)                                                                   Cyanuric                                                                            Aniline-3-sulphonic                                                                       nicotinic acid                      1,5-disulphonic acid                                                                        ethyl-6-hydroxy-4-methyl-                                                                    Chloride                                                                            acid                                                        2-oxo-1H pyridine (I)                                                          1-beta-(sulphatoethylamino)                                                    ethyl-6-hydroxy-4-methyl-                                                      2-oxo-1H pyridine (II)                                                         I 70% II 30%                                                 26   2-aminonaphthalene-                                                                         1-beta-(hydroxyethylamino)                                                                   Cyanuric                                                                            Aniline-4-sulphonic                                                                       nicotinic acid                      1,5-disulphonic acid                                                                        ethyl-6-hydroxy-4-methyl-                                                                    Chloride                                                                            acid                                                        2-oxo-1H pyridine (I)                                                          1-beta-(sulphatoethylamino)                                                    ethyl-6-hydroxy-4-methyl-                                                      2-oxo-1H pyridine (II)                                                         I 70% II 30%                                                 27   2-aminonaphthalene-                                                                         1-beta-(hydroxyethylamino)                                                                   Cyanuric                                                                            2-carboxyaniline-                                                                         iso-nicotinic                       1,5-disulphonic acid                                                                        ethyl-6-hydroxy-4-methyl-                                                                    Chloride                                                                            4-sulphonic acid                                                                          acid                                             2-oxo-1H pyridine (I)                                                          1-beta-(sulphatoethylamino)                                                    ethyl-6-hydroxy-4-methyl-                                                      2-oxo-1H pyridine (II)                                                         I 70% II 30%                                                 28   2-aminonaphthalene-                                                                         1-beta-(hydroxyethylamino)                                                                   Cyanuric                                                                            2-carboxyaniline-                                                                         iso-nicotinic                       1,5-disulphonic acid                                                                        ethyl-6-hydroxy-4-methyl-                                                                    Chloride                                                                            5-sulphonic acid                                                                          acid                                             2-oxo-1H pyridine (I)                                                          1-beta-(sulphatoethylamino)                                                    ethyl-6-hydroxy-4-methyl-                                                      2-oxo-1H pyridine (II)                                                         I 70% II 30%                                                 29   2-aminonaphthalene-                                                                         1-beta-(hydroxyethylamino)                                                                   Cyanuric                                                                            2-carboxyaniline-                                                                         iso-nicotinic                       1-disulphonic acid                                                                          ethyl-6-hydroxy-4-methyl-                                                                    Chloride                                                                            5-sulphonic acid                                                                          acid                                             2-oxo-1H pyridine (I)                                                          1-beta-(sulphatoethylamino)                                                    ethyl-6-hydroxy-4-methyl-                                                      2-oxo-1H pyridine (II)                                                         I 70% II 30%                                                 30   2-aminonaphthalene-                                                                         1-beta-(hydroxyethylamino)                                                                   Cyanuric                                                                            Aniline-2,4-di-                                                                           iso-nicotinic                       1-disulphonic acid                                                                          ethyl-6-hydroxy-4-methyl-                                                                    Chloride                                                                            sulphonic acid                                                                            acid                                             2-oxo-1H pyridine (I)                                                          1-beta-(sulphatoethylamino)                                                    ethyl-6-hydroxy-4-methyl-                                                      2-oxo-1H pyridine (II)                                                         I 70% II 30%                                                 31   2-aminonaphthalene-                                                                         1-beta-(hydroxyethylamino)                                                                   Cyanuric                                                                            Aniline-2,5-di-                                                                           nicotinic acid                      1-disulphonic acid                                                                          ethyl-6-hydroxy-4-methyl-                                                                    Chloride                                                                            sulphonic acid                                              2-oxo-1H pyridine (I)                                                          1-beta-(sulphatoethylamino)                                                    ethyl-6-hydroxy-4-methyl-                                                      2-oxo-1H pyridine (II)                                                         I 70% II 30%                                                 32   2-aminonaphthalene-                                                                         1-beta-(hydroxyethylamino)                                                                   Cyanuric                                                                            2-methylaniline-                                                                          nicotinic acid                      1-disulphonic acid                                                                          ethyl-6-hydroxy-4-methyl-                                                                    Chloride                                                                            4-sulphonic acid                                            2-oxo-1H pyridine (I)                                                          1-beta-(sulphatoethylamino)                                                    ethyl-6-hydroxy-4-methyl-                                                      2-oxo-1H pyridine (II)                                                         I 70% II 30%                                                 33   2-aminonaphthalene-                                                                         1-beta-(hydroxyethylamino)                                                                   Cyanuric                                                                            2-methylaniline-                                                                          nicotinic acid                      1,5-disulphonic acid                                                                        ethyl-6-hydroxy-4-methyl-                                                                    Chloride                                                                            5-sulphonic acid                                            2-oxo-1H pyridine (I)                                                          1-beta-(sulphatoethylamino)                                                    ethyl-6-hydroxy-4-methyl-                                                      2-oxo-1H pyridine (II)                                                         I 70% II 30%                                                 34   2-aminonaphthalene-                                                                         1-beta-(hydroxyethylamino)                                                                   Cyanuric                                                                            2-methylaniline                                                                           nicotinic acid                      1,5-disulphonic acid                                                                        ethyl-6-hydroxy-4-methyl-                                                                    Chloride                                                         2-oxo-1H pyridine (I)                                                          1-beta-(sulphatoethylamino)                                                    ethyl-6-hydroxy-4-methyl-                                                      2-oxo-1H pyridine (II)                                                         I 70% II 30%                                                 35   2-aminonaphthalene-                                                                         1-beta-(hydroxyethylamino)                                                                   Cyanuric                                                                            N-methylaniline                                                                           nicotinic acid                      1,5-disulphonic acid                                                                        ethyl-6-hydroxy-4-methyl-                                                                    Chloride                                                         2-oxo-1H pyridine (I)                                                          1-beta-(sulphatoethylamino)                                                    ethyl-6-hydroxy-4-methyl-                                                      2-oxo-1H pyridine (II)                                                         I 70% II 30%                                                 36   2-aminonaphthalene-                                                                         I 70% II 30%  Methoxy-                                                                            --         --                                  1,5,7-disulphonic acid     dichloro                                                                       triazine                                       37   2-aminonaphthalene-                                                                         I 70% II 30%  Methoxy-                                                                            --         --                                  3,6,8-trisulphonic acid    dichloro                                                                       triazine                                       38   2-aminonaphthalene-                                                                         I 70% II 30%  Cyanuric                                                                            aniline    nicotinic acid                      4,8-disulphonic acid       Chloride                                       39   2-aminonaphthalene-                                                                         I 70% II 30%  Cyanuric                                                                            aniline-2,4-di-                                                                           nicotinic acid                      6-sulphonic acid           Chloride                                                                            sulphonic acid                            40   2-aminonaphthalene-                                                                         I 70% II 30%  Cyanuric                                                                            aniline N-W-methane                                                                       nicotinic acid                      1,5-disulphonic acid       Chloride                                                                            sulphonate                                41   2-aminonaphthalene-                                                                         I 80% II 20%  Cyanuric                                                                            3-aminophenylsulphato                                                                     --                                  1,5-disulphonic acid       Chloride                                                                            ethylsulphone                             42   2-aminonaphthalene-                                                                         I 80% II 20%  Cyanuric                                                                            4-aminophenylsulphato                                                                     --                                  1,5-disulphonic acid       Chloride                                                                            ethylsulphone                             43   1-aminonaphthalene-                                                                         I 80% II 20%  Cyanuric                                                                            4,4'-diaminostilbene                                                                      iso-nicotinc                        4,8-disulphonic acid       Chloride                                                                            2,2'-disulphonic acid                                                                     acid                           44   1-aminonaphthalene-                                                                         I 80% II 20%  Cyanuric                                                                            4,4'-diaminostilbene                                                                      iso-nicotinc                        2,5,7-trisulphonic acid    Chloride                                                                            2,2'-disulphonic acid                                                                     acid                           __________________________________________________________________________ 

I claim:
 1. A water-soluble compound of formula (3) or salt thereof: ##STR9## A is a phenyl or naphthyl group which is unsubstituted or substituted by one or more substituent selected from --Cl, --Br, --C₁₋₄ -alkyl, --OH, --O--C₁₋₄ -alkyl, --CN, --NO₂, --NH₂, --NHCOCH₃, sulpho and carboxy;T¹ and T² are each independently H, CN, CO₂ R², CONR² R³, CONR² R³, COR², alkyl, aralkyl, cycloalkyl or aryl; Z is a divalent aliphatic radical containing from 2 to 6 carbon atoms; n is from 2 to 6; R¹ is H or sulpho; R² and R³ are each independently H or C₁₋₆ -alkyl; R⁴ and R⁵ are each independently H or C₁₋₄ -alkyl or R⁴ and R⁵ together with N-L-N form a piperazine ring; W is halo or quaternary ammonium; and L is a divalent aliphatic radical containing from 2 to 6 carbon atoms, --C₆ H₄.CH₂ --, --CH₂ C₆ H₄ CH₂ --, phenylene or naphthylene, said phenylene or naphthylene being unsubstituted or substituted by nitro, sulpho, lower alkoxy, carboxy or halo, or a divalent radical of the formula: ##STR10## wherein B is --S--, --O--, --SO₂ --, --CO--, --CH₂ --, --CH₂ CH₂ --, --NH--, --NHCONH--, a direct link or --CH═CH--, and the phenyl rings attached to B are unsubstituted or substituted by a COOH, methyl, nitro, chloro or sulpho atom or group.
 2. A compound according to claim 1 wherein L is ethylene, trimethylene, methylethylene, tetramethylene, alpha:beta-dimethylethylene, hexamethylene, --C₆ H₄.CH₂ --, --C₂ C₆ H₄ CH₂ --, 1,3- or 1,4-phenylene, 2-nitro-1,4-phenylene, 3-sulpho-1,4-phenylene, 4-methoxy-1,3-phenylene, 4-sulpho-1,3-phenylene, 4-nitro-1,3-phenylene, 2-carboxy-1,4-phenylene, 2-chloro-1,4-phenylene, 4-carboxy-1,3-phenylene, 3,7-disulpho-1,5-naphthylene, 2-methoxy-1,4-phenylene, or a group of formula: ##STR11## wherein B is --S--, --O--, --SO₂ --, --CO--, --CH₂ --, --CH₂ CH₂ --, --NH--, NHCONH--, a first direct link or --CH═CH--, and the phenyl rings attached to B are unsubstituted or substituted by a COOH, methyl, nitro, chloro or sulpho atom or group.
 3. A compound according to claim 2 wherein L is 2,2'-disulphostilbene-4,4'-yl.
 4. A compound according to claim 2 wherein R¹ is sulpho.
 5. A compound according to claim 2 wherein Z is --CH₂ C₂ --, --CH₂ CH₂ CH₂ --, --CH₂ CH(CH₃)CH₂ -- or --CH₂ CH₂ CH₂ CH₂ CH₂ --.
 6. A water-soluble compound of Formula (3) or salt thereof. ##STR12## wherein: A is phenylene or naphthylene, which is unsubstituted or substituted by a --Cl, --Br, --C₁₋₄ -alkyl, --OH, --O--C₁₋₄ -- alkyl, --CN, --NO₂, --NH₂, --NHCOCH₃, sulpho or carboxy group;T¹ and T² are each independently H, CN, CO₂ R², CONR² R³ or COR² ; Z is C₁₋₄ -alkylene; n is from 2 to 6; R¹ is H or sulpho; R² and R³ are each independently H or C₁₋₄ -alkyl; R⁴ and R⁵ are each independently H or C₁₋₄ -alkyl; W is halo, 3-carboxypyridinium or 4-carboxypyridinium; and L is of the formula: ##STR13## wherein B is --S--, --O--, --SO₂ --, --CO--, --CH₂ --, --CH₂ CH₂ --, --NH--, NHCONH--, a direct link or --CH═CH--, and the phenyl rings attached to B are unsubstituted or substituted by a COOH, methyl, nitro, chloro or sulpho atom or group.
 7. A water-soluble compound of Formula (3) or salt thereof ##STR14## wherein: A is phenylene or naphthylene, which is unsubstituted or substituted by a --Cl, --Br, --C₁₋₄ -alkyl, --OH, --O--C₁₋₄ --alkyl, --CN, --NO₂, --NH₂, --NHCOCH₃, sulpho or carboxy group;T¹ is C₁₋₄ -alkyl; T² H or Cl-4-alkyl; Z is --CH₂ CH₂ --, --CH₂ CH₂ CH₂ --, --CH₂ CH₂ (CH₃)CH₂ -- or --CH₂ CH₂ CH₂ CH₂ CH₂ --; n is from 2 to 6; R¹ is sulpho; R⁴ and R⁵ are each independently H or C₁₋₄ -alkyl; W is halo, 3-carboxypyridinium or 4-carboxypyridinium; and L is of the formula: ##STR15## wherein B is --S--, --O--, --SO₂ --, --CO--, --CH₂ --, --CH₂ CH₂ --, --NH--, NHCONH--, a direct link or --CH═CH--, and the phenyl rings attached to B are unsubstituted or substituted by a COOH, methyl, nitro, chloro or sulpho atom or group.
 8. A compound according to claim 7 wherein A is phenylene, naphthylene, phenylene substituted by a sulpho group or naphthylene substituted by a sulpho group.
 9. A compound according to claim 7 wherein R¹ is sulpho.
 10. A compound of Formula (6) or salt thereof ##STR16## wherein R¹ is H is sulpho; andW is halo, 3-carboxypyridinium or 4-carboxypyridinium.
 11. A compound according to claim 10 wherein L is 2,2'-disulphostilben-4,4'-yl. 